BR112018070035B1 - FILAMENT BASED ON PROPYLENE FOR 3D PRINTER - Google Patents

FILAMENT BASED ON PROPYLENE FOR 3D PRINTER Download PDF

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BR112018070035B1
BR112018070035B1 BR112018070035-5A BR112018070035A BR112018070035B1 BR 112018070035 B1 BR112018070035 B1 BR 112018070035B1 BR 112018070035 A BR112018070035 A BR 112018070035A BR 112018070035 B1 BR112018070035 B1 BR 112018070035B1
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filament
consumable filament
ethylene
propylene copolymer
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BR112018070035A2 (en
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Roberto De Palo
Claudio Cavalieri
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Basell Poliolefine Italia S.R.L.
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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • D—TEXTILES; PAPER
    • D01—NATURAL OR MAN-MADE THREADS OR FIBRES; SPINNING
    • D01F—CHEMICAL FEATURES IN THE MANUFACTURE OF ARTIFICIAL FILAMENTS, THREADS, FIBRES, BRISTLES OR RIBBONS; APPARATUS SPECIALLY ADAPTED FOR THE MANUFACTURE OF CARBON FILAMENTS
    • D01F6/00—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof
    • D01F6/28—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D01F6/30—Monocomponent artificial filaments or the like of synthetic polymers; Manufacture thereof from copolymers obtained by reactions only involving carbon-to-carbon unsaturated bonds comprising olefins as the major constituent
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y70/00—Materials specially adapted for additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/04—Monomers containing three or four carbon atoms
    • C08F210/06—Propene
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C64/00—Additive manufacturing, i.e. manufacturing of three-dimensional [3D] objects by additive deposition, additive agglomeration or additive layering, e.g. by 3D printing, stereolithography or selective laser sintering
    • B29C64/10—Processes of additive manufacturing
    • B29C64/106—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material
    • B29C64/118—Processes of additive manufacturing using only liquids or viscous materials, e.g. depositing a continuous bead of viscous material using filamentary material being melted, e.g. fused deposition modelling [FDM]
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y30/00—Apparatus for additive manufacturing; Details thereof or accessories therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B33—ADDITIVE MANUFACTURING TECHNOLOGY
    • B33Y—ADDITIVE MANUFACTURING, i.e. MANUFACTURING OF THREE-DIMENSIONAL [3-D] OBJECTS BY ADDITIVE DEPOSITION, ADDITIVE AGGLOMERATION OR ADDITIVE LAYERING, e.g. BY 3-D PRINTING, STEREOLITHOGRAPHY OR SELECTIVE LASER SINTERING
    • B33Y80/00—Products made by additive manufacturing
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F210/00—Copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond
    • C08F210/16—Copolymers of ethene with alpha-alkenes, e.g. EP rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2500/00—Characteristics or properties of obtained polyolefins; Use thereof
    • C08F2500/12—Melt flow index or melt flow ratio

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  • Chemical & Material Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Engineering & Computer Science (AREA)
  • Medicinal Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Textile Engineering (AREA)
  • General Chemical & Material Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Artificial Filaments (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

Trata-se de um filamento consumível para uso em um sistema de fabricação de aditivo com base em extrusão que compreende um copolímero de etileno-propileno que tem: - teor de unidades derivadas de etileno que varia de 3,0% em peso a 12,0% em peso; - MFR L (Índice de Fluidez de acordo com ISO 1133, condição L, isto é, 230°C e 2,16 kg de carga) de 4 a 20 g/10 min; e - solúveis de xileno medidos a 25°C compreendidos entre 3% em peso e 30% em peso.It is a consumable filament for use in an extrusion-based additive manufacturing system comprising an ethylene-propylene copolymer that has: - ethylene-derived units content ranging from 3.0% by weight to 12, 0% by weight; - MFR L (Flow Index according to ISO 1133, condition L, ie 230°C and 2.16 kg load) from 4 to 20 g/10 min; and - xylene solubles measured at 25°C comprised between 3% by weight and 30% by weight.

Description

Campo da InvençãoField of Invention

[001] A presente revelação refere-se a um filamento que compreende um copolímero de etileno-propileno a ser usado em uma impressora 3D com base em extrusão.[001] The present disclosure relates to a filament comprising an ethylene-propylene copolymer to be used in an extrusion-based 3D printer.

Antecedentes da InvençãoBackground of the Invention

[002] Uma impressora 3D com base em extrusão é usada para construir um modelo em 3D de uma representação digital do modelo em 3D de um modo camada a camada através da extrusão de um material de modelagem fluidificável. Um filamento do material de modelagem é extrudado através de uma ponta carregada por uma cabeça de extrusão e é depositado como uma sequência de percursos em um substrato em um plano x-y. O material de modelagem extrudado se funde ao material de modelagem anteriormente depositado e solidifica com uma queda na temperatura. A posição da cabeça de extrusão em relação ao substrato é então incrementada ao longo de um eixo geométrico z (perpendicular ao plano x-y) e o processo é depois repetido para formar um modelo em 3D semelhante à representação digital. O movimento da cabeça de extrusão em relação ao substrato é realizado por controle de computador, de acordo com dados de construção que representam o modelo em 3D. Os dados de construção são obtidos repartindo-se inicialmente a representação digital do modelo em 3D em múltiplas camadas repartidas horizontalmente. Depois, para cada camada repartida, o computador hospedeiro gera uma trajetória de construção para depositar percursos de material de modelagem para formar o modelo em 3D.[002] An extrusion-based 3D printer is used to build a 3D model from a digital representation of the 3D model in a layer-by-layer fashion through the extrusion of a fluidizable modeling material. A filament of modeling material is extruded through a tip carried by an extrusion head and deposited as a sequence of paths onto a substrate in an x-y plane. The extruded modeling material melts to the previously deposited modeling material and solidifies with a drop in temperature. The position of the extrusion head relative to the substrate is then incremented along a z-axis (perpendicular to the x-y plane) and the process is then repeated to form a 3D model similar to the digital representation. The movement of the extrusion head in relation to the substrate is performed by computer control, according to construction data representing the 3D model. Construction data is obtained by initially splitting the digital representation of the 3D model into multiple layers spread out horizontally. Then, for each split layer, the host computer generates a build path to deposit modeling material paths to form the 3D model.

[003] No processo de impressão, o filamento tem evidentemente um papel importante, mudando o material do filamento, as propriedades estéticas e mecânicas finais da mudança de objeto finalizado. Geralmente na técnica, filamento de ácido poliláctico (PLA) ou acrilonitrila, butadieno, polímero de estireno (ABS) ou poliamidas são usados.[003] In the printing process, the filament evidently plays an important role, changing the material of the filament, the final aesthetic and mechanical properties of the final object change. Generally in the art, polylactic acid (PLA) or acrylonitrile filament, butadiene, styrene polymer (ABS) or polyamides are used.

[004] Uma das propriedades mais importantes de um filamento é diâmetro constante (geralmente 1,75 mm ou 3 mm), de outro modo não seria possível sintonizar de modo preciso a quantidade de material no objeto impresso. Essa propriedade não é facilmente alcançada e depende das características do polímero.[004] One of the most important properties of a filament is constant diameter (usually 1.75 mm or 3 mm), otherwise it would not be possible to precisely tune the amount of material in the printed object. This property is not easily achieved and depends on the polymer characteristics.

[005] Além disso, o filamento, uma vez preparado, precisa ser passível de impressão, isto é, deve ser possível alcançar uma boa adesão com a placa e entre as camadas.[005] In addition, the filament, once prepared, must be printable, that is, it must be possible to achieve good adhesion with the plate and between the layers.

[006] Polímeros à base de propileno foram propostos como polímeros adequados para fabricar filamentos, contudo, os testes realizados pelo requerente os filamentos à base de propileno disponíveis no mercado geram resultados ruins no teste de impressão.[006] Propylene-based polymers have been proposed as suitable polymers to manufacture filaments, however, tests performed by the applicant on commercially available propylene-based filaments yield poor results in the print test.

[007] Portanto, há necessidade de polímeros à base de propileno que possam ser usados como um filamento em uma impressora em 3D.[007] Therefore, there is a need for propylene-based polymers that can be used as a filament in a 3D printer.

Sumário da InvençãoSummary of the Invention

[008] O requerente constatou um filamento consumível para uso em um sistema de fabricação de aditivo com base em extrusão que compreende um copolímero de etileno-propileno que tem: - teor de unidades derivadas de etileno que varia de 3,0% em peso a 12,0 % em peso; - MFR L (Índice de Fluidez de acordo com ISO 1133, condição L, isto é, 230°C e 2,16 kg de carga) que varia de 4 a 20 g/10 min; e - solúveis de xileno medidos a 25°C compreendidos e ntre 3% em peso e 30% em peso.[008] The applicant has found a consumable filament for use in an extrusion-based additive manufacturing system that comprises an ethylene-propylene copolymer that has: - ethylene-derived unit content ranging from 3.0% by weight to 12.0% by weight; - MFR L (Flow Index according to ISO 1133, condition L, that is, 230°C and 2.16 kg load) ranging from 4 to 20 g/10 min; and - xylene solubles measured at 25°C between 3% by weight and 30% by weight.

Breve descrição dos desenhosBrief description of drawings

[009] A Figura 1 é a vista frontal da amostra usada nos testes de impressão dos exemplos. A medição é fornecida em mm, a amostra quando completamente impressa tem 5 mm de espessura.[009] Figure 1 is the front view of the sample used in the printing tests of the examples. Measurement is given in mm, the sample when fully printed is 5 mm thick.

Descrição Detalhada da InvençãoDetailed Description of the Invention

[010] O requerente constatou um filamento consumível para uso em um sistema de fabricação de aditivo com base em extrusão que compreende um copolímero de etileno-propileno que tem: - teor de unidades derivadas de etileno que varia de 3,0% em peso e 12,0% em peso; preferencialmente de 3,5% em peso a 10,0% em peso; mais preferencialmente de 3,8% em peso a 8,0% em peso; - MFR L (Índice de Fluidez de acordo com ISO 1133, condição L, isto é, 230°C e 2,16 kg de carga) de 4 a 20 g/10 min, preferencialmente de 5 a 10 g/10 min; mais preferencialmente de 6 a 8 g/10 min; e - solúveis de xileno medidos a 25°C compreendidos e ntre 3% em peso e 30% em peso; preferencialmente entre 4% em peso e 25% em peso.[010] The applicant has found a consumable filament for use in an extrusion-based additive manufacturing system that comprises an ethylene-propylene copolymer that has: - ethylene-derived unit content ranging from 3.0% by weight and 12.0% by weight; preferably from 3.5% by weight to 10.0% by weight; more preferably from 3.8% by weight to 8.0% by weight; - MFR L (Flow Index according to ISO 1133, condition L, ie 230°C and 2.16 kg load) from 4 to 20 g/10 min, preferably from 5 to 10 g/10 min; more preferably from 6 to 8 g/10 min; and - xylene solubles measured at 25°C comprised between 3% by weight and 30% by weight; preferably between 4% by weight and 25% by weight.

[011] O termo copolímero significa que o polímero é formado apenas por monômeros, propileno e etileno.[011] The term copolymer means that the polymer is formed only by monomers, propylene and ethylene.

[012] O copolímero propileno/etileno da presente invenção pode ser extrudado em um filamento que tem um diâmetro constante, sendo que o diâmetro do filamento é aquele usado na técnica tal como 1,75 mm ou 3 mm. Outros diâmetros possíveis podem também ser usados. A variação do diâmetro nominal é +/- 0,05 mm, preferencialmente, +/0,03 mm.[012] The propylene/ethylene copolymer of the present invention can be extruded into a filament having a constant diameter, the filament diameter being that used in the art such as 1.75 mm or 3 mm. Other possible diameters can also be used. The nominal diameter range is +/-0.05mm, preferably +/0.03mm.

[013] Quando materiais poliméricos amorfos, tais como resinas de acrilonitrila-butadieno-estireno (ABS) e resinas de policarbonato são usados os mesmos têm pouco ou nenhuma exigência de disposições de suas cadeias de polímero em seus estados sólidos. Isso reduz os efeitos de enrolamento e deformação plástica no modelo em 3D ou estrutura de suporte resultantes.[013] When amorphous polymeric materials such as acrylonitrile-butadiene-styrene (ABS) resins and polycarbonate resins are used they have little or no requirement for dispositions of their polymer chains in their solid states. This reduces the effects of curling and plastic deformation on the resulting 3D model or support structure.

[014] Polímero cristalino ou semicristalino exibe propriedades mecânicas superiores, mas devido à cristalinidade quando usado para construir modelo em 3D os mesmos mostram efeitos de encolhimento indesejáveis tanto quando o percurso extrudado é depositado para formar uma porção de uma camada de um modelo em 3D quanto quando o percurso é resfriado. Os efeitos de encolhimento geram polímeros cristalinos ou semicristalinos não utilizáveis para a construção de objeto 3D em um processo de fabricação de aditivo com base em extrusão.[014] Crystalline or semi-crystalline polymer exhibits superior mechanical properties, but due to crystallinity when used to build 3D model they show undesirable shrinkage effects both when the extruded path is deposited to form a portion of a 3D model layer and when the path is cooled. Shrinkage effects generate crystalline or semi-crystalline polymers not usable for 3D object construction in an extrusion-based additive manufacturing process.

[015] O requerente constatou que o copolímero de etileno- propileno da presente revelação pode ser vantajosamente usado para construir um modelo em 3D que compreende polímeros semicristalinos conforme mostrado pela quantidade de material solúvel de xileno.[015] Applicant has found that the ethylene-propylene copolymer of the present disclosure can be advantageously used to build a 3D model comprising semicrystalline polymers as shown by the amount of xylene soluble material.

[016] O copolímero de etileno-propileno da presente revelação está disponível no mercado. Exemplo de copolímero pode ser RP220M vendido junto à LyondellBasell, BOREALIS RD204 CF. Outro polímero similar possível é LyondellBasell CLYRELL RC 1908.[016] The ethylene-propylene copolymer of the present disclosure is commercially available. Example copolymer can be RP220M sold from LyondellBasell, BOREALIS RD204 CF. Another possible similar polymer is LyondellBasell CLYRELL RC 1908.

[017] O objeto de filamento da presente invenção pode conter adicionalmente aditivos normalmente usados na técnica tais como antioxidantes, agentes de deslizamento, estabilizadores de processo, antiácidos e nucleantes.[017] The filament object of the present invention may additionally contain additives commonly used in the art such as antioxidants, slip agents, process stabilizers, antacids and nucleants.

[018] O filamento pode conter adicionalmente cargas conhecidas na técnica tal como talco, carbonato de cálcio, wollastonita, fibras de vidro, esferas de vidro e graus derivados de carbono.[018] The filament may additionally contain fillers known in the art such as talc, calcium carbonate, wollastonite, glass fibers, glass beads and carbon-derived grades.

[019] Além disso, o filamento da presente invenção pode contém também pó de madeira, pó metálico, pó de mármore e materiais similares usados para obter objeto em 3D que tem aparências estéticas particulares ou mecânica aprimorada.[019] In addition, the filament of the present invention may also contain wood dust, metal dust, marble dust and similar materials used to obtain 3D objects that have particular aesthetic appearances or improved mechanics.

[020] Os exemplos a seguir são dados para ilustrar e não limitam a presente invenção.[020] The following examples are given to illustrate and do not limit the present invention.

ExemplosExamples

[021] Os dados dos materiais de polímero de propileno foram obtidos de acordo com os seguintes métodos: Fração solúvel de xileno a 25°C[021] Data on propylene polymer materials were obtained according to the following methods: Soluble fraction of xylene at 25°C

[022] A fração solúvel de xileno foi medida de acordo com ISO 16152, 2005, mas com os desvios a seguir (entre parênteses é o que é prescrito pelo ISO 16152)[022] Soluble fraction of xylene was measured in accordance with ISO 16152, 2005, but with the following deviations (in parentheses is what is prescribed by ISO 16152)

[023] O volume de solução é 250 ml (200 ml)[023] The volume of solution is 250 ml (200 ml)

[024] Durante o estágio de precipitação a 25°C por 30 mi n, a solução, para os 10 minutos finais, é mantida sob agitação por um agitador magnético (30 min, sem nenhuma agitação)[024] During the precipitation stage at 25°C for 30 min, the solution, for the final 10 minutes, is kept under stirring by a magnetic stirrer (30 min, without any stirring)

[025] A etapa de secagem final é realizada a vácuo a 70°C (100°C)[025] The final drying step is carried out under vacuum at 70°C (100°C)

[026] O teor da dita fração solúvel em xileno é expresso como uma porcentagem das 2,5 gramas originais e, então, pela diferença (complementar a 100), a % insolúvel em xileno[026] The content of said fraction soluble in xylene is expressed as a percentage of the original 2.5 grams and then, by the difference (complementary to 100), the % insoluble in xylene

[027] Teor de etileno (c2) RMN de 13C de copolímeros propileno/etileno[027] Ethylene content (c2) 13C NMR of propylene/ethylene copolymers

[028] Os espectros de RMN de 13C foram adquiridos em um espectrômetro Bruker AV-600 equipado com criossonda, em operação a 160,91 MHz no modo de transformada de Fourier a 120°C.[028] The 13C NMR spectra were acquired on a Bruker AV-600 spectrometer equipped with cryoprobe, operating at 160.91 MHz in Fourier transform mode at 120°C.

[029] O pico do carbono Sββ (nomenclatura de acordo com "Monomer Sequence Distribution in Ethylene-Propylene Rubber Measured by 13C NMR. 3. "Use of Reaction Probability Mode" C. J. Carman, R. A. Harrington e C. E. Wilkes, Macromolecules, 1977, 10, 536) foi usado como referência interna a 29,9 ppm. As amostras foram dissolvidas em 1,1,2,2-tetracloroetano-d2 a 120°C com uma concentração de 8% em peso/v. Cada espectro foi obtido com um pulso de 90°, 15 segundos de atraso entre pulsos e CPD pa ra remover o acoplamento 1H-13C. 512 transientes foram armazenados em 32K pontos de dados com o uso de uma janela espectral de 9.000 Hz.[029] The Sββ carbon peak (nomenclature according to "Monomer Sequence Distribution in Ethylene-Propylene Rubber Measured by 13C NMR. 3. "Use of Reaction Probability Mode" C. J. Carman, R. A. Harrington and C. E. Wilkes, Macromolecules, 1977, 10 , 536) was used as an internal reference at 29.9 ppm. Samples were dissolved in 1,1,2,2-tetrachloroethane-d2 at 120°C with a concentration of 8% w/v. Each spectrum was obtained with a 90° pulse, 15 second delay between pulses, and CPD to remove the 1H-13C coupling.512 transients were stored at 32K data points using a spectral window of 9000 Hz.

[030] As atribuições dos espectros, a avaliação da distribuição de tríade e da composição foram feitas de acordo com Kakugo ("Carbon- 13 NMR determination of monomer sequence distribution in ethylenepropylene copolymers prepared with δ-titanium trichloridediethylaluminum chloride" M. Kakugo, Y. Naito, K. Mizunuma e T. Miyatake, Macromolecules, 1982, 15, 1.150) com o uso das seguintes equações: PPP = 100 Tββ/S PPE = 100 Tβδ/S EPE = 100 Tδδ/S PEP = 100 Sββ/S PEE= 100 Sβδ/S EEE = 100 (0,25 SYδ+0,5 Sδδ)/S S = Tββ + Tβδ + Tδδ + Sββ + Sβδ + 0,25 SYδ + 0,5 Sδδ[030] Spectra assignments, triad distribution and composition evaluation were performed according to Kakugo ("Carbon-13 NMR determination of monomer sequence distribution in ethylene propylene copolymers prepared with δ-titanium trichloridediethylaluminum chloride" M. Kakugo, Y . Naito, K. Mizunuma and T. Miyatake, Macromolecules, 1982, 15, 1150) using the following equations: PPP = 100 Tββ/S PPE = 100 Tβδ/S EPE = 100 Tδδ/S PEP = 100 Sββ/S PEE= 100 Sβδ/S EEE = 100 (0.25 SYδ+0.5 Sδδ)/S S = Tββ + Tβδ + Tδδ + Sββ + Sβδ + 0.25 SYδ + 0.5 Sδδ

[031] A porcentagem molar do teor de etileno foi avaliada com o uso da seguinte equação:[031] The molar percentage of ethylene content was evaluated using the following equation:

[032] % de E em mol = 100 * [PEP+PEE+EEE]A porcentagem em peso do teor de etileno foi avaliada com o uso da seguinte equação: 100 * % de E em mol * MWE % de E em peso = % de E em mol * MWE +% de P em mol * MWP em que % de P em mol é a porcentagem molar do teor de propileno, enquanto MWE e MWP são os pesos moleculares de etileno e propileno, respectivamente.[032] % E in mol = 100 * [PEP+PEE+EEE]The weight percentage of the ethylene content was evaluated using the following equation: 100 * % E in mol * MWE % E in weight = Mol % E * MWE + Mol % P * MWP where Mol % P is the mole percent of the propylene content, while MWE and MWP are the molecular weights of ethylene and propylene, respectively.

[033] O produto da razão de reatividade r1 r2 foi calculado de acordo com Carman (C.J. Carman, R.A. Harrington e C.E. Wilkes, Macromolecules, 1977; 10, 536) como:

Figure img0001
[033] The product of the reactivity ratio r1 r2 was calculated according to Carman (CJ Carman, RA Harrington and CE Wilkes, Macromolecules, 1977; 10, 536) as:
Figure img0001

[034] A taticidade de sequências de propileno foi calculada como mm de teor a partir da razão entre o PPP mmTββ (28,90 a 29,65 ppm) e o Tββ total (29,80 a 28,37 ppm) Índice de Fluidez (MFR)[034] The tacticity of propylene sequences was calculated as mm of content from the ratio between the PPP mmTββ (28.90 to 29.65 ppm) and the total Tββ (29.80 to 28.37 ppm) Fluidity Index (MFR)

[035] O índice de fluidez MFR do polímero foi determinado de acordo com a ISO 1133 (230°C, 2,16 Kg).[035] The MFR melt index of the polymer was determined according to ISO 1133 (230°C, 2.16 Kg).

[036] Os polímeros a seguir foram usados PP1[036] The following polymers were used PP1

[037] Homopolímero de propileno que tem um MFR 6,5 e uma fração solúvel em xileno a 25°C de < 4% PP2[037] Propylene homopolymer that has an MFR 6.5 and a xylene-soluble fraction at 25°C of < 4% PP2

[038] Filamento comercial de diâmetro 1,75 mm, vendido com o nome PP REPRAP BLACK FILAMENT German RepRap PP Filament 600 g, um copolímero de etileno-propileno aleatório que tem um teor de etileno de 3% em peso um MFR de 2 dl/10 min e uma fração solúvel em xileno a 25°C de 6,2% em peso. PP3[038] Commercial filament with a diameter of 1.75 mm, sold under the name PP REPRAP BLACK FILAMENT German RepRap PP Filament 600 g, a random ethylene-propylene copolymer that has an ethylene content of 3% by weight and an MFR of 2 dl /10 min and a xylene soluble fraction at 25°C of 6.2% by weight. PP3

[039] Copolímero de etileno-propileno vendido com o nome MOPLEN RP220M é um copolímero de etileno-propileno aleatório que tem um teor de etileno de 4% em peso de um MFR de 7 e uma fração solúvel em xileno a 25°C de 7%[039] Ethylene-propylene copolymer sold under the name MOPLEN RP220M is a random ethylene-propylene copolymer that has an ethylene content of 4% by weight of an MFR of 7 and a xylene-soluble fraction at 25°C of 7 %

[040] Polímeros PP1 e PP3 foram extrudados para formar um filamento que tem 1,75 mm de diâmetro. A fim de ter capacidade para extrudar PP1, 10% em peso de talco foi adicionado. Teste de impressão[040] Polymers PP1 and PP3 were extruded to form a filament that is 1.75 mm in diameter. In order to be able to extrude PP1, 10% by weight of talc was added. print test

[041] A impressora foi uma impressora 3D Rostock delta. As condições da impressora são as seguintes:

Figure img0002
Figure img0003
[041] The printer was a Rostock delta 3D printer. Printer conditions are as follows:
Figure img0002
Figure img0003

[042] A amostra a ser impressa é reportada na Figura 1. Para cada filamento, 5 testes de impressora foram realizados, e a impressão foi interrompida quando um lado do objeto é destacado do plano e, portanto, a impressão do objeto não foi mais possível. Os resultados são reportados na Tabela 1

Figure img0004
* comparativo[042] The sample to be printed is reported in Figure 1. For each filament, 5 printer tests were performed, and the printing was stopped when one side of the object is detached from the plane and therefore, the printing of the object was no longer possible. The results are reported in Table 1
Figure img0004
* comparative

[043] A partir da Tabela 1, é evidente que apenas PP3, que é o material de acordo com a invenção, pode ser usado para imprimir completamente a amostra.[043] From Table 1, it is evident that only PP3, which is the material according to the invention, can be used to completely print the sample.

Claims (11)

1. Uso de um filamento consumível caracterizado pelo fato de que compreende um copolímero de etileno-propileno que tem: - teor de unidades derivadas de etileno que varia de 3,0% em peso a 12,0 % em peso; - MFR L (Índice de Fluidez de acordo com ISO 1133, condição L, isto é, 230°C e 2,16 k g de carga) de 4 a 20 g/10 min; e - solúveis de xileno medidos a 25°C compreendidos e ntre 3% em peso e 30% em peso; em um sistema de fabricação de aditivo com base em extrusão.1. Use of a consumable filament characterized in that it comprises an ethylene-propylene copolymer which has: - content of ethylene-derived units ranging from 3.0% by weight to 12.0% by weight; - MFR L (Flow Index according to ISO 1133, condition L, ie 230°C and 2.16 kg load) from 4 to 20 g/10 min; and - xylene solubles measured at 25°C comprised between 3% by weight and 30% by weight; in an extrusion-based additive manufacturing system. 2. Uso do filamento consumível, de acordo com a reivindicação 1, caracterizado pelo fato de que, no copolímero de propileno, o teor de unidades derivadas de etileno varia de 3,5% em peso e 10,0% em peso.2. Use of the consumable filament, according to claim 1, characterized in that, in the propylene copolymer, the content of ethylene-derived units varies from 3.5% by weight to 10.0% by weight. 3. Uso do filamento consumível, de acordo com a reivindicação 1 ou 2, caracterizado pelo fato de que o copolímero de propileno tem um MFR L (Índice de Fluidez de acordo com ISO 1133, condição L, isto é, 230°C e 2,16 kg de carga) que varia de 5 a 10 g/10 min.3. Use of the consumable filament, according to claim 1 or 2, characterized in that the propylene copolymer has an MFR L (Flow Index according to ISO 1133, condition L, that is, 230°C and 2 .16 kg load) which varies from 5 to 10 g/10 min. 4. Uso do filamento consumível, de acordo com qualquer uma das reivindicações 1 a 3, caracterizado pelo fato de que, no copolímero de propileno, os solúveis de xileno medidos a 25°C são compreendidos entre 4% em peso e 25% em peso.4. Use of the consumable filament, according to any one of claims 1 to 3, characterized in that, in the propylene copolymer, the xylene solubles measured at 25°C are comprised between 4% by weight and 25% by weight . 5. Uso do filamento consumível, de acordo com qualquer uma das reivindicações 1 a 4, caracterizado pelo fato de que, no copolímero de propileno, o teor de unidades derivadas de etileno varia de 3,8% em peso a 8,0% em peso.5. Use of the consumable filament, according to any one of claims 1 to 4, characterized in that, in the propylene copolymer, the content of ethylene-derived units varies from 3.8% by weight to 8.0% by Weight. 6. Uso do filamento consumível, de acordo com a reivindicação 1 ou 5, caracterizado pelo fato de que o copolímero de propileno tem um MFR L (Índice de Fluidez de acordo com ISO 1133, condição L, isto é, 230°C e 2,16 kg de carga) que varia de 6 a 8 g/10 min.6. Use of the consumable filament, according to claim 1 or 5, characterized in that the propylene copolymer has an MFR L (Flow Index according to ISO 1133, condition L, that is, 230°C and 2 .16 kg load) which varies from 6 to 8 g/10 min. 7. Uso do filamento consumível, de acordo com qualquer uma das reivindicações 1 a 6, caracterizado pelo fato de que o filamento consumível tem um diâmetro constante que tem uma variação de +/0,05 mm.7. Use of the consumable filament, according to any one of claims 1 to 6, characterized in that the consumable filament has a constant diameter that has a variation of +/0.05 mm. 8. Uso do filamento consumível, de acordo com qualquer uma das reivindicações 1 a 7, caracterizado pelo fato de que o filamento consumível tem um diâmetro constante que tem uma variação de +/0,03 mm.8. Use of the consumable filament, according to any one of claims 1 to 7, characterized in that the consumable filament has a constant diameter that varies by +/0.03 mm. 9. Uso do filamento consumível, de acordo com qualquer uma das reivindicações 1 a 8, caracterizado pelo fato de que o filamento consumível tem um diâmetro de 1,75 mm ou 3 mm +/- 0,05 mm.9. Use of the consumable filament, according to any one of claims 1 to 8, characterized in that the consumable filament has a diameter of 1.75 mm or 3 mm +/- 0.05 mm. 10. Uso do filamento consumível, de acordo com qualquer uma das reivindicações 1 a 8, caracterizado pelo fato de que o filamento consumível tem um diâmetro de 1,75 mm ou 3 mm +/- 0,03 mm.10. Use of the consumable filament, according to any one of claims 1 to 8, characterized in that the consumable filament has a diameter of 1.75 mm or 3 mm +/- 0.03 mm. 11. Uso do filamento consumível, de acordo com a reivindicação 1 a 10, caracterizado pelo fato de que é para a produção de artigos impressos em 3D.11. Use of consumable filament, according to claims 1 to 10, characterized in that it is for the production of 3D printed articles.
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